Ethyl ether from ethylene

Isopropyl Ether. Isopropyl ether is manufactured by the dehydration of isopropyl alcohol with sulfuric acid. It is obtained in large quantities as a by-product in the manufacture of isopropyl alcohol from propylene by the sulfuric acid process, very similar to the production of ethyl ether from ethylene. Isopropyl ether is of moderate importance as an industrial solvent, since its boiling point Hes between that of ethyl ether and acetone. Isopropyl ether very readily forms hazardous peroxides and hydroperoxides, much more so than other ethers. However, this tendency can be controlled with commercial antioxidant additives. Therefore, it is also being promoted as another possible ether to be used in gasoline (33). 

Hydration of Ethyl Ether. Using the same type of acid catalysts as in the hydration of ethylene to ethanol, ethyl ether can be hydrated to the alcohol. Catalysts that have been used for the hydration of ether include phosphoric acid (144), sulfuric acid (145,146), hydrochloric acid (147), metallic oxides (141,148,149) and sihcates (150). Sulfuric acid concentrations ranging from 5—25% at 200°C (144) to 63—70% at 110—135°C and 1.01—1.42 MPa (10—14 atm) (148) have been claimed. 

Ethyl Ether. Most ethyl ether is obtained as a by-product of ethanol synthesis via the direct hydration of ethylene. The procedure used for production of diethyl ether [60-29-7] from ethanol and sulfuric acid is essentially the same as that first described in 1809 (340). The chemical reactions involved in the production of ethyl ether by the indirect ethanol-from-ethylene process are like those for the production of ether from ethanol using sulfuric acid. 

C) Preparation of 2-Methyl-3-(2,2,2-Trifluoroethyl)Thiomethyl-6-Chloro-7-Sulfamyl-3,4-Dihydro-1,2,4-Benzothiadiazine-1,1-Dioxide To 4.6 g (0.015 mol) of 4-amino-2-chloro-5-(methylsulfamyl)benzenesulfonamide in 30 ml of the dimethyl ether of ethylene glycol is added 4.08 g (0.02 mol) of 2,2,2-trifluoroethylmercaptoacetaldehyde dimethylacetal followed by 1 ml of ethyl acetate saturated with hydrogen chloride gas. The resulting solution is refluxed for 1.5 hours, cooled and then slowly added to cold water dropwise with stirring. The crude product is filtered, dried and recrystallized from isopropanol (3.2 g), MP 202° to 202.5°C. A second recrystallization from isopropanol raised the MP to 202°... 

Materials and Purification. Chemicals were purchased from Aldrich chemical company and used as received unless otherwise noted 1,1,1,3,3,3-hexamethyl disilazane, ethylene glycol, triphosgene, poly(ethylene oxide) (MW = 600), poly(tetramethylene oxide) (MW = 1000), poly(caprolactonediol) (MW = 530), toluene diisocyanate (TDI), anhydrous ethanol (Barker Analyzed), L-lysine monohydride (Sigma) and methylene bis-4-phenyl isocyanate (MDI) (Kodak). Ethyl ether (Barker Analyzer), triethylamine and dimethyl acetamide were respectively dried with sodium, calcium hydride and barium oxide overnight, and then distilled. Thionyl chloride and diethylphosphite were distilled before use. 

Source Bis(2-chloroethyl) ether does not occur naturally in the environment. In Canada, this compound enters the environment as a by-product from chlorination of waste streams containing ethylene, propylene (Environment Canada, 1993) or ethyl ether (quoted, Verschueren, 1983). 

These reactiona exhibit a great difference between the behaviour of ethylenic ether and that of ethylic ether. This difference arises from the fact that in ethylic ether the ethyl atoms are held together by the oxygen only, whereas in ethylenic ether the link-ing of the atoms of CH, does not depend on the oxygen atom alone, os will be seen from the Mowing formula —... 

For example, carbon dioxide from air or ethylene nitrogen oxides from nitrogen methanol from ethyl ether. In general, carbon dioxide, carbon monoxide, ammonia, hydrogen sulphide, mercaptans, ethane, ethylene, acetylene, propane and propylene are readily removed at 25°. In mixtures of gases, the more polar ones are preferentially adsorbed). 

Ethylene carbonate (l,3-dioxalan-2-one) [96-49-1] M 88.1, m 37", d 1.32, n 1.4199. Dried over P2O5 then fractionally distd at 10mm pressure. Crystd from dry ethyl ether. 

Ethylene dimyristate [627-84-9] M 482.8, m 61.7 . Crystd from benzene-MeOH or ethyl ether-MeOH, and dried in a vacuum desiccator. 

Traditionally, ethanol has been made from ethylene by sulfation followed by hydrolysis of the ethyl sulfate so produced. This type of process has the disadvantages of severe corrosion problems, the requirement for sulfuric acid reconcentration, and loss of yield caused by ethyl ether formation. Recently a successful direct catalytic hydration of ethylene has been accomplished on a commercial scale. This process, developed by Veba-Chemie in Germany, uses a fixed bed catalytic reaction system. Although direct hydration plants have been operated by Shell Chemical and Texas Eastman, Veba claims technical and economic superiority because of new catalyst developments. Because of its economic superiority, it is now replacing the sulfuric acid based process and has been licensed to British Petroleum in the United Kingdom, Publicker Industries in the United States, and others. By including ethanol dehydrogenation facilities, Veba claims that acetaldehyde can be produced indirectly from ethylene by this combined process at costs competitive with the catalytic oxidation of ethylene. 

DEHYDRATION (Chemical). Removal of water from a substance or system or chemical compound or removal of the elements of water, in correct proportion, from a chemical compound or compounds. The elements of water may be removed from a single molecule, or from more than one molecule, as in the dehydration of alcohol this may yield ethylene, by loss of the elements of water from each molecule, or ethyl ether, by loss of the elements of water from two molecules, which then join to form a new compound ... 

As many as 70 products were at one time produced commercially from ethanol. Some of these downstream products are butanol, 2-ethyl hexanol, crotonaldehyde, butyraldehyde, acetaldehyde, acetic acid, butadiene, sorbic acid, 2-ethylbutanol, ethyl ether, many esters, ethanol-glycol ethers, acetic anhydride, vinyl acetate, ethyl vinyl ether, even ethylene gas. Many of these products are now more economically made from other feedstocks such as ethylene for acetaldehyde and methanol-carbon monoxide for acetic acid. Time will tell when a revival of biologically-oriented processes will offer lower-cost routes to at least the simpler products. 

Material. Diethyl ether shall be made from ethyl alcohol conforming to the requirements for grade 1 or grade 2 of Specification MIL-A-463 (See in this Vol under Ethanol), or ether shall be made as a co-product in the manuf of Ethanol from ethylene... 

The decomposition of acetaldehyde, sensitized by biacetyl, was studied at 499 °C by Rice and Walters , and between 410 and 490 °C by Boyer et al. They found the initial rate to be proportional to the square root of the biacetyl concentration and to the first power of the aldehyde concentration. The chains are initiated by the radicals originating from the decomposition of the biacetyl molecule. The decomposition of acetaldehyde can be induced also by di-r-butyl peroxide (at 150-210 °C, about 10-50 molecules decompose per peroxide molecule added), as well as by ethylene oxide (around 450 °C each added ethylene oxide molecule brings about the decomposition of up to 300 acetaldehyde molecules). For the influence of added diethylether, vinyl ethyl ether, ethyl bromide, and ethyl iodide etc., see Steacie °. 

In addition to the intact residues of 2,4,5-T excreted in the rat urine, mass spectral evidence was obtained for the presence of the metabolite TCP and a trichlorodihydroxybenzene isomer, which were observed as their mono- and diethyl ether derivatives, respectively. Thus, TCP ethyl ether displayed a molecular ion at m/e 224 and characteristic fragments at m/e 196 and m/e 160 owing to consecutive elimination of ethylene and HCl from the parent ion. The fragmentation pattern of 2,4,5-tri-chloropenol was observed to exhibit similar behavior below m/e 196. 

One of the most interesting papers on ascorbic acid-Cu reactions showed that ascorbic acid-Cu catalyzes the formation of ethylene from several precursors. The interest in ethylene was as an abscission agent in plants. All alcohols, aldehydes, acids, ethers, and epoxides formed ethylene when mixed with Cu and ascorbic acid in 5-mL closed bottles at 30 °C for 1 h. Methional was the most active, followed by propanal, propanol, propyl ether, ethyl ether, and ethanol. This reaction may be part of the oxygen scavenging system because Cu increases ascorbic acid s ability to scavenge oxygen. The authors claim this reaction cannot be attributed to copper in its lower valence state. 

Sample preparation and derivatization methods for GC analysis of BAs have been also proposed. In a method developed by Daudt and Ough (1980), amines are distilled from the alkalized grape juice or wine sample and trapped in an acidified solution. After concentration under vacuum, methylamine, dimethylamine, ethylamine, diethylamine, n-propylamine, isobutylamine, a-amylamine, isoamylamine, pyrrolidine, and 2-phenethylamine in their salt form are derivatized with triflu-oroacetic (TFA) anhydride. TFA derivatives are extracted with ethyl ether and analyzed by GC-MS with a capillary fused silica poly( ethylene) glycol (PEG) column and the following oven temperature program 8 min at 70 °C, l°C/min to 160 °C, isotherm for 90 min. 

Methylmorphenol is also obtained as the final product of exhaustive methylation of codeine ethiodide [10], y-codeimethine (the C-6 epimer of [m]) [11] and e-codeimethine methyl ether [vn, R = CH3] (obtained by the degradation of (/(-codeine methyl ether [vi, R = CH3]) [12-13] the other substances produced during the degradation of [vn, R = CH3] are trimethylamine, ethylene, and methyl alcohol [12], 1-Bromomethyl-morphenol [vin] arises in like manner by the degradation of 1-bromo-codeine [10, 14-16] and ethylmorphenol from morphine-3-ethyl ether [17]. 

Apparently, no attempts have been made to determine accurately the equilibria at various temperatures for the dehydration reaction, possibly because of the difficulties involved in the prevention of complicating side reactions which are invariably present in the temperature range involved, approach to the equilibrium from the hydration of ethylene side is impractical since ethylene has been found to hydrate with considerable difficulty in the vapor phase. Also, the formation of ethyl ether has been found to occur over a wide range of temperatures and is a complicating factor, especially at the lower temperatures. 

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